Process for generating hydrocarbon free radicals from carboxylic acids as tertiary alcohols

ABSTRACT

Certain organic reactants which are free from aliphatic unsaturation and which are capable of yielding free radicals upon treatment with peroxides are oxidized, in the liquid phase in an aqueous medium, with certain peroxy compounds to form freeradical intermediates which are then allowed to react further with themselves or with other components of the reaction medium to form useful end products. Preferred features include the slow addition of the peroxy compound to the reaction zone and the use of certain metalic ions to improve yields. The process may be used for the reaction of HCN and carboxylic acids to produce nitriles; the conversion of tertiary alkanols to ketones; and the production of cyanogen from hydrogen cyanide.

United States Patent [72] Inventor Alexander F. MacLean Durham,N.ll.

21 App1.No. 795.031

[22] Filed Jan.29.1969

[4S] Patented Nov.9,1971

[73] Assignee CelaneseCorporation New York. N.Y.

Continuation-impart of application Ser. No. 333,751. Dec. 26, 1967, now abandoned.

[52] U.S.Cl 23/151,

260/4653. 50/483, 260/5 26 R. 260/540. 260/593 R. 260/652, 260/676 R. 260/681,

3 60/593 R. 595. 596, 465.3. 65 2. 483. 526 R, 540. 676 R. 681, 682

[56] References Cited UNITED STATES PATENTS 2.647.920 8/1953 Patrick.Jr. etal 260/483 2.802.020 8/1957 Fierce et a1. 23/151 2.818.441 12/1957 Vaughan et a1 260/632 2.883.426 4/1959 Brackman 260/596 3,110,722 11/1963 Bruckman 260/464 3.347.643 10/1967 Nielsen 23/357 OTHER REFERENCES Kirk-Othmer. Encyclopedia of Chemical Technology," Vol. 10. pg. 38. pp. 47- 48(19531'1191568 Primary Examiner-Oscar R. Vertiz Assislanl Examiner-H0ke S. Miller A1mrne vs Marvin Turken. Stewart N. Rice and Ralph M.

Pritchett ABSTRACT: Certain organic reactants which are free from aliphatic unsaturation and which are capable of yielding free radicals upon treatment with peroxides are oxidized. in the liquid phase in an aqueous medium. with certain peroxy compounds to form free-radical intermediates which are then allowed to react further with themselves or with other components of the reaction medium to form useful end products. Preferred features include the slow addition oi the peroxy compound to the reaction zone and the use of certain metalic ions to improve yields. The process may be used for the reaction of HCN and carboxylic acids to produce nitriles; the conversion of tertiary alkanols to ketones; and the production of cyanogen from hydrogen cyanide.

PROCESS FOR GENERATING HYDROCARBON FREE RADICALS FROM CARBOXYLIC ACIDS AS TERTIARY ALCOHOLS This is a continuation-in-part of application Ser. No. 33,751, filed Dec. 26, 1963 and now abandoned.

This invention relates broadly to a method of effecting a chemical reaction. The invention is especially concerned with certain new and useful improvements in a method of synthesizing organic compounds by a chemical reaction involving reactable material. including essentially at least one organic reactant, more particularly a tertiary alcohol. an organic acid, a salt of an organic acid, or a combination of such an acid and a salt in any proportions. The organic reactant is further characterized by the fact that it is free from aliphatic unsaturation, and is capable of yielding free organic radicals, more particularly hydrocarbon radicals, under free-radical forming conditions.

One embodiment of the present invention comprises evolving free organic radicals, e.g., hydrocarbon radicals, from organic-reactant material ofthe kind abovedescribed by oxidizing the latter under free radical-forming conditions in an aqueous or aqueous-organic solvent medium with an inorganic peroxy compound, more particularly an inorganic peroxy acid (inorganic peroxide) or its salt wherein the reaction is carried out by slow addition" of the peroxy compound, such that the peroxy concentration never exceeds one-third the concentration which would be obtained by batchwise addition of all the peroxy compound, determined by iodometric titration of a sample.

THe inorganic peroxy compounds found to be useful are those which may be represented by the general formula AO'O A where A and A may be the same or different and each represents a member of the group consisting of (HO),-PO', HO-(CO)-, HO-(SO but not H; and salts of the peroxides embraced by the aforementioned formulas, especially those which are at least partly soluble in water or in a mixture or water and an organic solvent. More specific examples of such inorganic persalts are, for instance, the alkali'metal and ammonium persulfates, percarbonates and perphosphates. Peroxides (or their salts) of organic carboxylic acids and hydrogen peroxide are not satisfactory for use in practicing the present invention.

In accordance with another aspect of the invention, the oxidation to free radicals can be effected in the presence of a salt, such as silver salt, to catalyze the formation of the radical and improve the yield of desired products and in the presence of other salts, such as a copper salt, to promote a specific reaction ofthe free radical so released.

Using the methods of this invention. it has been found that acetic acid is oxidized to carbon dioxide plus methane, ethane, and methyl acetate by potassium persulfate, In the presence of hydrogen cyanide, acetonitrile is obtained.

Another example is the oxidation of propionic acid to carbon dioxide plus butane, ethane, ethylene, propionitrile. ethyl chloride and ethanol.

All of the products obtained by persulfate oxidation can be explained on the basis that the carboxylic acid is oxidized to a free radical and on the reactions ofsuch free radicals.

In the method ofthis invention carboxylic acids and tertiary alcohols, for example, are oxidized to free radicals by peroxides such as potassium persulfate. The persulfate ion oxidizes the organic acid, or its ion to a free radical intermediate; 1, 2.

The organic intermediate free radical R-COO- is not stable and decomposes as in equation 3. 3. R'COO R +CO.

When the persulfate is added batchwise to the carboxylic acid or its salt yields of desired products were low but when it was added slowly the yields were much increased. The slow addition was done so that the persulfate reacted as it was added and its concentration in the reaction mixtures never exceeded one-third the concentration which would have resulted from batch mixing.

Operating at increased temperature or in the presence of Ag ions with slow addition of persulfate also increases the yield because they increase the relative rate of 8,0,, decomposition and cause it to be maintained at a lower steady state concentration. Silver introduces a chain reaction involving the reduction of S 0 shown in equations 4 and 5. 4. 0,. Ag 0,, Ag 5. Ag R'COO' RCOO- Ag The S0, still reacts by equation 3 so the stoichiometry and products are not changed by the addition of Ag. It might be reasoned that the Ag from equation 4 would oxidize R- from equation 3, This reaction does not appear to proceed despite the high oxidation potential of Ag. It is known that ions, such as Cu with much lower oxidation potentials will oxidize R.

The radicals R- generated by the slow addition of persulfate react in the ways anticipated. Alkyl radicals disproportionate, condense or abstract hydrogen. The course depends on the nature of the radical, their steady state concentration or the presence or absence of abstractable hydrogen atoms. The reactions are illustrated by equations 6, 7 and 8. 6. 2R CH- h; R-CH -CH R-CHrCH, 7. 2R'CH -CH (R-CH a lCH 8. R-CH 'CH R'II R-CH 'CH R Ifa large excess of acetic acid were used, for instance, CH radicals would be the primary products. These would react with the excess of acetic acid to yield succinic acid. These reactions are shown in equations 9, l0, and 11. 9. CH -COO--'CH;,- +CO 10. CH,- +CH -,-CO0H -CH COOH CH ll. ZCH COOH HOOC CH 'CH COOH If the concentration of acetic were low ethane would be the main product. 12. 2'CH,-,CH 'CH:

In the presence of certain metal salts the radicals are oxidized. For instance acetic acid oxidized in the presence of cupric acetate will yield methyl acetate by oxidation of the methyl radical.

The C 0 (3 (.II; lI'OIll 13 is oxidized back to Cu (O O C CH3): by persulfate and the S 0 produced in this step introduces the new chain reaction as in equation 14.

Methyl radicals will react with other cupric salts. Cupric chloride yields methyl chloride and cupric cyanide yields acetonitrile.

Methyl radicals contain no alpha carbon hydrogen atoms so their reactions are least complex. Ethyl radicals made by the oxidation of propionic acid can undergo disproportionation and ionic deprotonation so their reactions are more complex. The disproportionation of ethyl radicals yields ethane and ethylene. l5 CH 'CH CH -CH CH :CH Ethyl radicals in the presence of cupric salts can undergo deprotonation or radical substitution depending on the salt ligand. Cupric acetate yields ethylene and cupric cyanide yields propionitrile.

The reactions are shown in equations 16 and 17.

0 16. CH -CIIg-+Cu(OCCHah-tCHyCH;+CuOCCH -l-CII COOI[ l7. CH -CH '+Cu(CN) CH;,-CH 'CN+Cu CN Tertiary alcohols on oxidation of the alcohol give an oxy radical precursor which will decompose to a ketone and a free radical. Tertiary butanol yielded acetone and methane and probably a tetra methyl butyene glycol. These reactions are illustrated by equations l8, I9, 20 and 21.

(lit

The overall stoichiometry of the various reactions is shown below. Radical Condensation 22. +2Kl-lSO Hydrogen Abstraction 23. 2ROOCH+2HCY +K S O, *2 RH+2CO +2KHSO +2 -CY Radical Disproportionation (for CH Cl-hCOOH) 24. 2CH CH -COOH'HQS O, Cl i zCli -eCl-l -CH,,+2CO ZKSO, Radical Substitution 25. R-COOH+HX+K S O,,Cu*E-X+CO,+2KHSO Radical Deprotonation 26. CH *CH COOH+K S O,,Cu**CH :CH +CO +2KHSO,

Radical substitution was observed with cyanide salts in lower yields. In the absence ofcupric salts nitrile radicals were probably mad in low yields and these combined directly with the radicals from the carboxylic acid. In the case ofacetic acid this reaction would be 27 and 28. 27. SO,--+-CN SOT +-CN 28. -CN-lCl-l,, CH CN When a copper is present a complex is favored between this radical and the salt and will decompose by deprotonation depending on the radical attached to the copper.

From the foregoing, it will be seen that the present invention provides a new and unobvious method of producing a great variety of organic compounds. For example, by reaction equation when X=CN a series of nitrile compounds such as acetonitrile, benzonitrile, or valeronitrille can be made. Chlorides and alcohols can also be made when X=Cl or X=OH. Under certain conditions, esters can be made where X=RCOOO. Another example is the generation of vinyl olefins by reaction (26). Thus, heptanoic acid would yield hexene-l, and cyclo-hexane carboxylic acid would yield cyclohexene.

illustrative examples of organic acids (or salts thereof) that may be used in practicing the present invention are the various straightor branched-chain monobasic acids. more particularly monocarboxylic acids, and especially the saturated aliphatic and the aromatic monocarboxylic acids such, for example, as those represented by the general formula R-COOH, where R represents a hydrocarbyl radical, more particularly a saturated aliphatic (including cycloaliphatic) or aromatic hydrocarbon radical, e.g. methyl through octadecyl, cyclohexyl, cycloheptyl, phenyl, tolyl, benzyl, phenylethyl and others. Examples of such acids are the C through C monocarboxylic acids, both straightand branched-chain. Polybasic acids, more particularly polycarboxylic acids, also may be employed. Examples of such acids include malonic, succinic, glutaric, adipic, pimelic, suberic, sebacic, tricarboxyklic, and others wherein the carboxylic groups are attached directly to a saturated aliphatic or aromatic hydrocarbon residue. in some cases it may be desirable to use an anhydride of a monoor polycarboxylic acid instead of part or all of such an acid.

Salts of organic acids may be used in place of or in addition to the acid and/or anhydride itself. The salts employed are preferably those which are at least partly soluble in water and will ionize in water. The cation of such salts may be, for instance, any of the alkali metals, barium, strontium, calcium, magnesium, copper, nickel, silver and others that form salts with a carboxylic acid that are at least partly soluble in water.

instead of using a single organic acid and a single organic salt one can use a plurality of organic acids and/or a plurality of the same or different salts of said acids.

As indicated hereinbcfore, a tertiary alcohol can be used as an organic reactant in practicing the present invention. Thus one may use a tertiary-alkanol such as tertiary-butanol. Such alkanols, which can be oxidized to hydrocarbon radicals, may be represented by the general formula where R, R and R" are the same or different alkyl radicals. Preferably the various R's represent a lower alkyl radical, more particularly methyl through hexyl. Thus each of the various R's can be a methyl radical and the fonnula then becomes that of tertiary-butanol which evolves methyl radicals upon oxidation in accordance with this invention. Of course it will be understood by those skilled in the art that the various R's in the above formula may be an alkyl radical higher than C radicals, e.g., up to C or C or even higher radicals, depending upon such considerations as availability or ease of manufacture. and the particular end-products desired.

Taking chloroacetic acid and succinic acid as illustrative of the organic acids employed, the free or initiating radicals that are evolved are CICH and 'CH 'CH COOl-i, respectively. Other examples will be apparent to those skilled in the art from the examples of starting reactants given hereinbefore and in the examples that follow.

CONDITIONS OF REACTION The reaction is effected in an aqueous reaction medium, e.g., water alone or a mixture of water and an organic solvent which is miscible with water or at least partly soluble in water. e.g., acetonitrile, dioxane. or acetone or water mixed with the acid being oxidized. Preferably water alone is used. in general, the reaction will proceed at a satisfactory rate below the boiling point of the aqueous solution. and the reaction temperature can be decreased further in the presence of silver, copper or other catalyst salts. The reaction medium may constitute, for instance, from about an equal part by weight of the reactants to about 50 times their weight, or even higher, as desired or as conditions may require.

Tee temperature of the reaction may be varied, for example, from about ambient temperature (2030 C.), preferably at least about 40 C., to about C. The use of higher temperatures, is, of course, not precluded. This may be desirable when using more stable peroxides or to obtain low reaction time.

The peroxide is added continuously to the other reactants at such a rate that the steady state concentration of the peroxide remains at a value less than one-third that which would result from batch mixing advantages were observed for slow addition of the peroxide to the organic compound to be oxidized over batch addition.

The molar ratios of reactants may be varied considerably. Usually the ratios are such that the proportion oforganic reactant, (e.g., organic acid and/or salt thereof) to peroxy compound used in practicing this invention is within the range of, for example, about 1 to 50 moles of the former per mole of the latter. When an additional reactant or reactants are included with those just named, e.g., a nitrile, it is generally employed in an amount which is in a mole ratio in excess of the peroxide from 1 to 10.

As indicated hereinbefore, the oxidation reactions with which this invention is concerned can be effected in the presence or absence of a catalyst for the reaction, more particularly a catalyst comprising at least one metallic ion. The amount of such catalyst may range from a trace up to, for example, lO mole percent of the molar amount of the other active reactants employed. The use of larger molar amounts is not precluded.

SALT ION Ag CO (Silver carbonate) Ag Cu(OAc),-H,O tCupric Acetate) Cu Co(OAc),H,O (Cobaltous Acetate) Co Ni(OAc) H O (Nickelous acetate) Ni Hg(OAc) (Mercuric acetate) Hg H PtCl,, -6HO (Chloroplalinic acid) PtCl Ce (CO,) -5H,O (Cerrous carbonate) Ce CetS J: (Cerric s lfate) Ce Cr(OAc) (Chromic acetate) plus H O Cr" Similarly other ions, e.g., iron and manganese ions, as well as other ions may be introduced into the reaction mass. Salts other than the particular salts of the metals just mentioned may be employed.

In order that those skilled in the art may better understand how the present invention can be carried into effect, the following examples are given by way of illustration and not by way of limitation. All parts and percentages are by weight unless otherwise stated.

The runs of table I of example I, run ILA of table II, and run III-A of table 111 were made as follows. In batch tests the amounts of reactants shown were charged to a jacketed reactor. The reaction temperature was controlled by refluxing a liquid, which boiled at the desired reaction temperature, in the reactor jacket. (Benzene was the refluxing liquid in the runs of example I to maintain a reaction temperature of 80 C.; and acetone in example III-A to maintain a reaction temperature of 56 C.) The free space of the reactor was kept low to prevent dilution of the gas sample. The gas was passed through a sampling tube to a leveling gas receiver to prevent pressure buildup. The liquid in the leveling tube was saturated aqueous MgSO The gas was analyzed by mass spectrography.

In the foregoing and most of the other runs that were made. the amounts of liquid product were. in general. not determined because oftheir low concentration.

The runs where the liquid volume exceeded 120 CC. were made as follows. The reactor was a flask of suitable volume equipped with a thermometer. dropping funnel and reflux condenser. The flask was charged with the starting ingredients, more particularly in these runs with water. acetic acid and/or sodium acetate. HCN (in some runs) and. in most 5 runs. a catalyst or combination of catalysts. The reaction mixture was heated to about 98 C.. and 100 cc. of aqueous 0.2 M potassium persulfate was added. In those marked slow addn. it was added at a fairly constant rate over a period of 30 minutes. In those marked batch". all the potassium persulfate solution was added initially to the reactor with the other ingredients. the liquid product was analyzed by gasliquid partition chromatography immediately after the run.

Example 1 TAB LE 1 Example l ll Reactants. moles:

AcONa 'Iimc. minutes. Temperature,

(0. of solution 100 100 110 H of product 1.0 13.0 T. 7 l). s 4. 7 Batch or slow addition Batch Batch Batch Batch Batch Products, molcs/ mole X18105:

EXAMPLE 11 This example shows the effect of silver catalysis on the yield of methyl radicals and the effect of slow addition of potassium persulfate as compared to the batch reaction.

Example I1-A shows that silver ions promote the oxidation of acetic acid to methyl radicals and lower the reaction temperature from to 31 C. (see example lD for comparison). Presumably. the persulfate oxidizes the silver and this oxidizes the acetate ion (equations 4 and 5 Example "-8 shows that the yield of methyl radicals and their products in the presence ofsilver ions is increased significantly by the slow addition of potassium persulfate to acetic acid at C. as compared to the batch addition at 31 C. Although the methane yield is over double. the ethane yield declined. This was caused by the lower steady state concentration of the methyl radicals which tended to reduce condensation to ethane (equation 12) and reaction with the persulfate ion. Example ll-C shows that the presence of added sodium acetate in acetic acid causes a decrease in the methyl radical yield when Ag ions are present. The sodium acetate would increase the pH. THis would decrease the activity of silver as a persulfate decomposition catalyst and thereby decrease the catalytic effect of silver.

EXAMPLE Ill This example shows the effect of cupric ions on methyl radicals.

TABLE 111 Example 111 A 111 It 111 III I [ll 1' Roactants. molcs:

X28 05. 0.03 0.02 0.0: 0.02 0.0: AcON-a t). 1: 0. ()5 0. 05 0. 05 0, [)5 H O 5.5 5.5 5.5 5.!) 5.5 A0011 0. 05 0. 05 0. 05 0. 05 Catalyst. moles Cu++ 0. 0015 0. 000004 0. 00002 0. 0002 TlIlIt.IIlllll1LtS :7 30 311 30 311 Temperature, T5 100 100 100 100 Cc. olsolutiou 110 111) 110 Ill) Batch 01' slow addition Batch ('1 l l Products. inohs niolv K2S-: s

.- 0. 015 0. 73 0. 223 0. 053 0.00 0. 000 0. 073 0. 018 0. 00!) 0. 00 0. J15 1. 05 1. 04 0. 5 4 0. Kl) 0. 040 0. 000 0. 51 0. (i4 0. 75

1 Slow addition.

TAB LE Examplv. Y A \'-lt \'-l) Rvnctants, 11101014:

KzS U ll U. H. U. 0,02 0,02 ACUNtL. (7. (if) it. ()5 (l. 05 ll, [I5 A]! 0.10 0,10 0.10 0.10 lltN... 0.04 0.04 0,04 0,04 H 0 .1.5 u. u. .5 u. 5 tutalysts, 1110105.. ('o r Ni a l'tClttl. ill "00-! ll. 00U25 U. 0003 Ti1t1v,t11i11utcs..... 30 30 3U 3U Tmnpcmiurv. 100 100 100 100 (0. 0| solution 175 175 175 I75 Hatch or slow addition H Products. mnlcfmolt- RS 0 C(),=..... 1.635 (LM 1.605 1.546 CH; 0, 575 0.135 0.15 U. 575 (1H5 0. 00 (l. Oil ll. 00 0. ()0 (CN); 0.020 0.055 (1.345 0.20 ClIaCX (l. 165 0. .li5 l). 1!! ll. 22 CHsOAC 0.010 0.010 0.015 0.020

1 Ctr+ 0.000004, A 0.0007. Slow addition Example ll-A shows that the batchwise decomposition of copper salts. It caused the one-half time to decrease from 42 minutes at 80 C. to 7 minutes at 75 C. (see example l-E for comparison). Copper enters into a cycle of oxidation and reduction reactions which increase the rate (equations i3. 14,

Example lV-A shows that. in the absence of a catalyst. lower yields are obtained, probably by combination of free nitrile and methyl radicals. Example IV-B shows the yields of acetonitrile. cyanogen and methyl acetate are all increased by copper. The acetonitrile is presumably formed through the methyl carbonium-copper l, 2, and 3). Examples llI-B to Ill-E show the effect of in 25 creasing amounts of copper ions on the formation of methyl acetate, presumably through the methyl carbonium-copper EXAMPLE v acetate complex intermediate.

The limiting yield of carbon dioxide and methyl acetate when these are the only products is 1.0 mo e per o o THis example shows that sodium acetate and hydrogen cyapOta ium p r l lf qu o 25} WhBre R=CH3 and nide are oxidized to cyanogen plus acetonitrile by the slow ad- X=CH 'o0. EXAMPLE lV dition of potassium persulfate. The yield is increased to vary- This example shows tha mlxtures f 1166116 c ydr ge ing degrees by the addition of various ions. Copper is the most cyanide and the1r salts are oxidized to a mixture of cyanogen, ff tiv t l Sodium a etate plus a eti a id is ethane. acetonitrile, and methyl acetate. f bl to acetic id TABLE [V The catalysts and the percent of theoretlcal acetomtnle Example lV-A TV-B yield are;

Reuctants. moles 40 Camus Yield 10.5.0, 0.02 0.0: Mom. 0.05 0.10 AcOH 0.10 0.10 235 HCH 0.04 0.04 Hg .4 ,0 9.5 9.5 Catalyst. moles 0.000004 4 Time. min. 30 30 2:" Temperature. C I00 I00 cc. of Solution I80 I80 Batch or Slow Addn. Slow Addn. Slow Addn. Products. mole/mole x s o. (:0 1.70 1.11 EXAMPLE V1 C0. 001: 0.18 0.11.. 0.00 0.00 (CN 0.02 0.02:0 CHJCN 0.135 0.64 Th1s example shows the products obtained from ethyl radt- CH OAc 0.010 0.030 Ca|5 TABLE \1 Example VI-A \"I-B V -0 V I-D \'IE VI-F \'I G Reactants, moles:

N aOH to pH Catalyst, moles:

Batch or slow addit10n Batch Products, mole/mole X18205:

H (l. 0t 00 0.01 0. 56 (J. 000 0.000 0. 036 l). 02 1. 46 0. 14 O. 005 0. 315 0. 173 0. 0O 0. 05 0. 02 0. 01 0. 02 0. 09 0.10 1. J7 1. 05 0. 865 1. 000 0. 962 0. 025 O. 035 0. 021 3 11 0}! 0.115 0. 205 O. 485

* Slow addition.

Example Vl-A shows that sodium propionate is oxidized to ethyl radicals and carbon dioxide. The ethyl radicals abstract hydrogen to yield ehtane (equation 8 where R=H) or disproportionate to yield ethane and ehylene (equation 6 where R=H). Example Vl-B shows that the yield of carbon dioxide and radicals is much lower when propionic acid is oxidized. Example Vl-C shows that when silver ions are present propionic acid is oxidized in high yields to ethyl radicals and carbon dioxide. The yield of ethane is high but ethylene low. The disproportionation reaction (equation 6) to produce ehtylene and ethane is low here because the steady state concentration of ethylene is kept at a low steady state by Slow addition of the potassium persulfate. Example Vl-D shows that in the presence of both copper and silver ions significant yields of ethylene are obtained. In this case the copper ions deprotonate the ethyl radicals to ethylene (equations 16). The limiting yield of ethylene is 1 mole per mole of potassium persulfate (equation 26). Example VlE shows that when mixtures of sodium cyanide, sodium propionate, and propionic acid are oxidized, some propionitrile is made as well as smaller amounts of ethane and cyanogen. These products are obtained by combination of nitrile and ethyl radicals (equations 27 and 28 where CH;,'=C H Example Vl-F shows that the yields of all the products obtained in Vl-E are increased by the addition of silver ions. Silver is presumably a better catalyst for generating nitrile and ethyl radicals (Ag+CN' Ag +-CN and equations and 3). Example Vl-G shows that the yield of propionitrile is significantly increased and ethylene is also made by the combined efi ect of copper and silver over the effect of silver alone. The yields of cyanogen and ethane are decreased. In the presence of copper salts the ethyl radicals deprotonate (equation 29A.R=CH;,-CH or substitute (equation 29-B,R=CH;,-CH For copper cyanide the substitution is favored over the deprotonation by ratio of 0.485 with ethyl radicals. The maximum yield of deprotonation by a ratio of 0.485 with ethyl radicals. The maximum yield of deprotonation or substitution products by copper catalysis is l0 mole of CO and 1.0 mole radical conversion product for 1.0 mole ofperoxide (equation and 26).

EXAMPLE Vll TABLE \'II YlI-B Example s VII-A \'IIC React-ants, moles: K283 a. This quantity of caustic was added continuously during the runs (as a 1.0 N solution) to maintain the pH at the given value. The pH was maintained constant at this value throughout the run.

b. The hydroxide ion amounts are reported as molar concentrations. These figures were obtained from the following formula:

l0 is the ionization constant of water at C.

PrOH-Progaionic Acid PrOHa-Sodium Propionaic Et. Ethyl radical Elf-Ethyl carbonium ion A silver catalyst was used in examples Vll-A, B and C to increase the ethyl radical yield.

Example Vll-A shows the effect of sulfate ions on the ethyl radicals. Some ethanol is made. Presumably the ethyl carbonium ion-copper sulfate complex yields some ethyl sulfate which hydrolyzes to ethanol (equation 298). Only 6.9 percent of the carbonium complex yields ethyl sulfate. The remainder is deprotonated to ethylene (equation 28A Example Vll-B shows that phosphate ions have an effect very similar to sulfate ions. The ethyl phosphate intermediate would hydrolyze to ethanol. Only 4.0 percent of the carbonium ion is substituted. Example Vll-C shows that perchlorate ions show only 2.8 percent substitution of the carbonium ion. Example VllD shows that the carbonium copper chloride complex is 68.7 percent converted to ethyl chloride plus ethanol. The major substitution product is the chloride by a ratio of 16 to l.

Example Vii-E shows that the carbonium copper hydroxide complex is 53 percent converted to ethanol. in this run on the alkaline side only percent of the ethyl radical passed through the copper salt-carbonium ion complex. in the others.

hydroxyl radicals which preferentially react with additional hydrogen peroxide to form oxygen and water rather than with an organic reactant to form intermediate organic radicals capable of further reacting to form organic products.

h v l averaged b w about 36 d about 55 percent, 5 it is to be understood that the foregoing detailed description is given merely by way of illustration and that many variations X PLE v1" may be made therein without departing from the spirit of our invention.

This example shows the products obtained by the oxidation I claim: ofions other than acetic or propionic by potassium persulfate. l l. In the art of organic chemical synthesis involving chemi- TABLE VIII Example VIII-A (1114i VIII-C \III-l) \III-i-l \'II1-F Rcactnms, moles:

Adiplc acid KCN 2S0; i s i t t t-CdhOll Catalyst, moles:

Ag O. 007 0. 014 0. OH

Cu I. 010 Tii11u,z1iinutcs 120 80 Temperature. C 100 mu Cc. of solution.. 110 :00 500 500 Batch or slow addition Batch Slow Slow Slow Products. lllOl0.'Il10lC CH2= CIl-CO CIIa-CIIr-COOIL. Butadienc 130 TU IOU 83 1.50 .330 ow Slow lllfi Example Vlll-A shows that formic acid is oxidized to carbon dioxide. Example Vlll-B shows that butyric acid yields propylene. The ethane and ethylene were not expected. Example Vlll-C shows the products expected from the postulated CH -CH -COOH intermediate radical. They are acrylic acid by deprotonation and propionic acid by hydrogen abstraction. Example Vlll-D shows the expected five carbon acids. They should be a mixture of 4-pentenoic acid and pentaneoic acid. in addition, some butadiene was observed. This would have been obtained by secondary oxidation of the pentenoic acid to the butene radical, CH :CH .CH .CH and deprotonation of this radical to butadiene. Example Vill-E shows that hydrogen cyanide (in the presence of excess sulfuric acid potassium cyanide gives cyanogen) is oxidized to cyanogen in 50 percent of theoretical yield. Example VIII-F shows that tertiary butyl alcohol is oxidized to acetone and methane. This is explained on the basis ofa tertiary-butoxy intermediate radical (equations 1, l8,and l9).

lt will be understood, of course, by those skilled in the art that the present invention is not limited only to the specific ingredients, proportions thereof, time, temperature and other conditions of reaction that have been given in the foregoing examples and detailed description by way of illustration. For instance, instead of potassium persulfate one may use any other alkali-metal persulfate or ammonium persulfate, or the corresponding percarbonates or perphosphates, or the corresponding available peracids. Likewise, other organic acids. salts of organic acids, tertiary alcohols. nitriles, catalysts and other additives including other reactants may be used in lieu of or in addition to those employed in the individual examples. Numerous examples of such other components have been given hereinbefore.

As has been stated previously, the process of this invention does not include the use of hydrogen peroxide or organic peroxides or hydroperoxides as the peroxy compound which could be employed. The reason for this is that these peroxy cally reactive material including essentially at least one or ganic reactant which is free from aliphatic unsaturation, is capable of yielding free organic radicals under free radicalforming conditions, and is selected from the group consisting of tertiary alcohols, organic acids and salts of organic acids, the improvement which consists in evolving from said organic reactant free organic radicals by oxidizing said organic reactant in a liquid medium comprising water, under free radicalforming conditions with at least one peroxy compound selected from the group consisting of (a) peroxy acids represented by the general formula A'O-O-A' where A and A each represents a member of the group consisting of (HO); PO, HO-(CO)- and HO-(SO.;)., and (b) salts of the peroxy acids of (a); said peroxy compound being added to the reaction zone such that its concentration never exceeds one-third that which would result from batchwise addition of all the peroxy compound utilized; and allowing the said evolved organic radicals to enter into an electron pairing reaction with a coreactant which is a compound having in the molecule a moiety having electron pairing propensities.

2. The improvement as in claim I wherein the peroxy compound is a salt of the peroxy acid of(a) said salt being at least partly soluble in water.

3. The improvement as in claim 1 wherein the peroxy compound is an alkali-metal persulfate.

4. The improvement as in claim 3 wherein the alkali-metal persulfate is potassium persulfate.

5. The improvement as in claim I wherein the organic reactant is tertiary butanol.

6. The improvement as in claim 1 wherein the organic reactant comprises a saturated aliphatic carboxylic acid.

7. The improvement as in claim 1 wherein the organic reactant comprises a salt ofa saturated aliphatic carboxylic acid.

8. The improvement as in claim I wherein the organic reactant is oxidized in the presence ofa catalyst comprising at least one metallic ion.

9. The improvement as in claim 8 wherein the metallic ion comprises a copper ion.

10. The improvement as in claim 8 wherein the catalyst comprises both a copper ion and a silver ion.

11. The improvement as in claim I wherein, said member of said group is a salt.

12. The improvement as in claim ll wherein in addition to said salt. there is also employed the acid corresponding to said salt.

13. In the art of organic chemical synthesis involving at least two different chemically reactive materials. one of which is HCN and another of which comprises a monocarboxy compound that contains at least two carbon atoms is free from aliphatic unsaturation and is capable of yielding free hydrocarbon radicals under free radical-forming conditions, the improvement which consists in evolving free hydrocarbon radicals from said monocarboxy compound by oxidizing said compound under free radical-forming conditions in an aqueous medium containing a water-soluble persulfate; and isolating from the reaction mass a nitrile corresponding to the hydrocarbon radicals evolved.

14. The improvement as in claim 13 wherein the monocarboxy compound comprises acetic acid, the water-soluble persulfate is potassium persulfate, and the isolated nitrile is acetonitrile.

15. The method of producing a ketone which comprises oxidizing a tertiary alkanol by bringing it into reactive relationship in a liquid medium comprising water with at least one peroxy compound selected from the group consisting of (a) peroxy acids represented by the general formula ADO-A where A and A each represents a member of the group consisting of (HOE-PO; HO'(CO)' and HO'(S'O.,)-. and (b) salts ofthe acids of(a).

16. The method of producing acetone which comprises oxidizing tertiary butanol with a water-soluble persulfate in an aqueous medium.

17. The method which comprises oxidizing an acid represented by the general formula H'X where X is a member of the group consisting of Cl. -Br and 'CN together with an organic acid or salt of an organic acid said reactants yielding .X and ,R radicals respectively under free-radical forming conditions by bringing said acids into reactive relationship in a liquid medium comprising water with at least one peroxy com pound selected from the group consisting of (a) peroxy acids represented by the general formula A-O-O-A' where A and A each represents a member of the group consisting of (HO) :PO-. HO-(CO)-, and HO-(SO and (b) salts of the acids of (a) to form said radicals which combine to form a product comprising RX.

18. The method of producing cyanogen which comprises oxidizing HCN with a water-soluble persulfate in an aqueous medium.

19. The method of producing cyanogen which comprises oxidizing HCN with a water-soluble persulfate in an aqueous medium containing copper ions as a catalyst for the reaction. 

2. The improvement as in claim 1 wherein the peroxy compound is a salt of the peroxy acid of (a) said salt being at least partly soluble in water.
 3. The improvement as in claim 1 wherein the peroxy compound is an alkali-metal persulfate.
 4. The improvement as in claim 3 wherein the alkali-metal persulfate is potassium persulfate.
 5. The improvement as in claim 1 wherein the organic reactant is tertiary butanol.
 6. The improvement as in claim 1 wherein the organic reactant comprises a saturated aliphatic carboxylic acid.
 7. The improvement as in claim 1 wherein the organic reactant comprises a salt of a saturated aliphatic carboxylic acid.
 8. The improvemenT as in claim 1 wherein the organic reactant is oxidized in the presence of a catalyst comprising at least one metallic ion.
 9. The improvement as in claim 8 wherein the metallic ion comprises a copper ion.
 10. The improvement as in claim 8 wherein the catalyst comprises both a copper ion and a silver ion.
 11. The improvement as in claim 1 wherein, said member of said group is a salt.
 12. The improvement as in claim 11 wherein, in addition to said salt, there is also employed the acid corresponding to said salt.
 13. In the art of organic chemical synthesis involving at least two different chemically reactive materials, one of which is HCN and another of which comprises a monocarboxy compound that contains at least two carbon atoms, is free from aliphatic unsaturation and is capable of yielding free hydrocarbon radicals under free radical-forming conditions, the improvement which consists in evolving free hydrocarbon radicals from said monocarboxy compound by oxidizing said compound under free radical-forming conditions in an aqueous medium containing a water-soluble persulfate; and isolating from the reaction mass a nitrile corresponding to the hydrocarbon radicals evolved.
 14. The improvement as in claim 13 wherein the monocarboxy compound comprises acetic acid, the water-soluble persulfate is potassium persulfate, and the isolated nitrile is acetonitrile.
 15. The method of producing a ketone which comprises oxidizing a tertiary alkanol by bringing it into reactive relationship in a liquid medium comprising water with at least one peroxy compound selected from the group consisting of (a) peroxy acids represented by the general formula A.O.O.A'' where A and A'' each represents a member of the group consisting of (HO)2.PO., HO.(CO). and HO.(SO2)., and (b) salts of the acids of (a).
 16. The method of producing acetone which comprises oxidizing tertiary butanol with a water-soluble persulfate in an aqueous medium.
 17. The method which comprises oxidizing an acid represented by the general formula H.X where X is a member of the group consisting of .Cl, .Br and .CN together with an organic acid or salt of an organic acid said reactants yielding .X and .R radicals respectively under free-radical forming conditions by bringing said acids into reactive relationship in a liquid medium comprising water with at least one peroxy compound selected from the group consisting of (a) peroxy acids represented by the general formula A.O.O.A'' where A and A'' each represents a member of the group consisting of (HO)2:PO., HO.(CO)., and HO.(SO2)., and (b) salts of the acids of (a) to form said radicals which combine to form a product comprising RX.
 18. The method of producing cyanogen which comprises oxidizing HCN with a water-soluble persulfate in an aqueous medium.
 19. The method of producing cyanogen which comprises oxidizing HCN with a water-soluble persulfate in an aqueous medium containing copper ions as a catalyst for the reaction. 